MgCl2/AlEtn(OEt)(3-n)负载[OSSO]型桥联双苯氧基钛催化剂催化乙烯聚合  

[OSSO]-type bis( phenolate) titanium complex for ethylene polymerization supported by MgCl_2/AlEt_n(OEt)_(3-n)

作　　者：龙永江[1] 梁华晴 周启花 魏婉楚[1] 祝方明[1,2] LONG Yongjiang LIANG Huaqing ZHOU Qihua WEI Wartchu ZHU Fangming(Guangdong Provincial Key Laboratory for High Performance Polymeric Composites, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China Key Laboratory for Polymer Composite and Functional Materials of Ministry of Education, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China)

机构地区：[1]中山大学化学学院广东省高性能树脂基复合材料重点实验室,广东广州5102751 [2]中山大学化学学院聚合物复合材料及功能材料教育部重点实验室,广东广州5102751

出　　处：《中山大学学报（自然科学版）》2017年第1期1-7,共7页Acta Scientiarum Naturalium Universitatis Sunyatseni

基　　金：国家自然科学基金(21174167,51573212);广东省自然科学基金(S2013030013474,2014A030313178)

摘　　要：以三乙基铝(AlEt_3)改性MgCl_2和乙醇(EtOH)的加合物(MgCl_2/nEtOH)为载体[MgCl_2/AlEt_n(OEt)_(3-n)]负载[OSSO]型桥联双苯氧基二氯化钛([OSSO]TiCl_2),制得乙烯聚合负载型催化剂;使用廉价易得的一氯二乙基铝(AlEt_2Cl)为助催化剂高效催化乙烯聚合,合成了以长支链为主的支化聚乙烯。探讨了MgCl_2/AlEt_n(OEt)_(3-n)载体的制备工艺、聚合条件对目标催化剂催化乙烯聚合行为以及聚合产物结构的影响。研究表明,负载型催化剂相对[OSSO]TiCl_2均相催化剂,催化乙烯聚合具有较高的活性,最高活性可达每106g(PE)/(mol(Ti)·h),比均相催化剂高百倍。13C NMR和DSC分析表明,负载型[OSSO]TiCl_2催化剂合成的聚乙烯为以长支链为主的支化聚乙烯,支化度(1 000个碳原子中支链的含量)为15,其中长支链含量为60.3%,熔融温度(Tm)为126℃,乙烯聚合反应速率逐渐升高后趋于平稳。The [OSSO]-type bis （phenolate）titanium complex （[OSSO]TiCl2 ）was supported by MgCl2/AlEtn （OEt）3-n and then used to efficiently promote the polymerization of ethylene under the acti-vation of the cheap diethylaluminum chloride （AlEt2 Cl ）. The resulted polymer was a long chain branched polyethylene.The influences of the preparation technology of support,triethyl aluminum modif-ying the adduct of MgCl2 and ethyl alcohol （EtOH）（MgCl2/AlEtn （OEt）3-n ）,and the polymerization conditions including polymerization temperature,ethylene press and Al （in AlEt2 Cl）∶Ti on the poly-merization behavior and the polymer structure were explored.The result indicated that the supported cata-lyst could more actively promote the polymerization of ethylene than the homogeneous catalyst with the highest activity of 1 06 g （PE）/（mol（Ti）·h）,which was hundredfold of the homogeneous catalyst.The a-nalysis of the 1 3 C nuclear magnetic resonance spectroscopy confirmed that the obtained polyethylene cata-lyzed by the supported catalyst was the long chain branched polyethylene with a branch number of 1 5 and a long branched chain content of 60.2%.The analysis of differential scanning calorimetry shows that the melting temperature of the branched polyethylene was 1 26 ℃.The kinetics of the ethylene polymerization was steady.

关 键 词：[OSSO]型桥联双苯氧基二氯化钛 负载型催化剂 支化聚乙烯 

分 类 号：O632.1[理学—高分子化学]